Natural and synthetic sodium sulfonate emulsifier blends

ABSTRACT

An emulsifier composition includes at least one natural alkali metal petroleum sulfonate and at least one synthetic alkali metal sulfonate. The emulsifier composition can be combined with a lubricant oil to provide a water-miscible lubricating oil concentrate which forms a stable aqueous emulsion upon the addition thereto of an aqueous medium.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims priority to U.S. provisional applicationSer. No. 60/653,685 filed Feb. 15, 2005 to which priority is claimed andwhich is herein incorporated by reference.

BACKGROUND

1. Field of the Invention

The present invention relates to an emulsifier composition including ablend of natural and synthetic sodium sulfonates.

2. Background of the Art

Sodium petroleum sulfonates are widely used as the primary emulsifier informulating emulsifiable lubricating compositions used for cuttingfluid, hydraulic fluids, metalworking lubricants, and so forth.

Sodium petroleum sulfonates are typically produced as a by-product ofrefining processes in which certain highly refined petroleum productssuch as white lubricating oils, medicinal oils, and certain grades oftransformer oils, are produced. The highly refined petroleum productsare produced by treating a refined petroleum distillate or raffinatewith fuming sulfuric acid which reacts with certain components of theoil to produce sulfonic acids, some of which are oil-soluble and some ofwhich are water-soluble, thus forming a two-phase system. The two phasesseparate into two layers one of which is the oil layer containing theoil-soluble reddish-brown or mahogany sulfonic acids, and one of whichis the water-soluble layer commonly referred to as an acid sludge layerthat contains resinous materials, unreacted sulfuric acid, andwater-soluble or green sulfonic acids. The layers are then separated andthe oil-soluble sulfonic acids are recovered from the oil layer, usuallyin the form of their sodium salts.

The mahogany sulfonic acids being preferentially oil-soluble have foundwide use in the preparation of emulsifiable petroleum products, such asin soluble cutting oils, hydraulic fluids, metalworking lubricatingfluids for forming of metals, and so forth. The acid oil layer isneutralized to make a sodium salt and extracted with a polar solvent,typically alcohol, to separate most of the oil phase, and to increasethe activity of the sodium sulfonate. This type of process is discussedgenerally in U.S. Pat. No. 1,930,488. The manufacture of white oils bythe above process has become increasingly uneconomical and as a result,the production of sulfonates as by-products of white oil refining issubstantially declining. This has left a significant shortage of sodiumpetroleum sulfonates.

Another major disadvantage with the natural petroleum sulfonates istheir inconsistency in quality, and hence a variance in theiremulsifying properties. In order to improve emulsification properties,secondary surface active agents of different types are often added, forinstance, fatty acid salts. The amount of the secondary surface activeagent used is varied depending on the quality of the sulfonate beingemployed. U.S. Pat. No. 4,140,642 describes an improved emulsifiercomposition in which salts of alkylaryl sulfonic acids are employed withan organic or mineral base, and in which the equivalent weights of theacids are distributed according to a function of C=f(M) where C denotesthe concentration and M denotes the equivalent weight of individualacids, which function has two distinct equivalent weight maximum M₁ andM₂, with M₁<M₂. Surprisingly, the present inventors have found a blendof sulfonates that provides an emulsifier composition that hasconsistent emulsification properties, and that is economical as well.This blend comprises at least one natural alkali metal petroleumsulfonate that is not prepared as a by-product of an oil refiningprocess and may be non-extracted, and a blend of other high activesynthetic sulfonates or sulfonic acids selected so as to produce anemulsification system that has 60% or greater active content, andselected so as to balance the oil solubility and emulsificationperformance thus providing an excellent surfactant system.

SUMMARY

An emulsifier composition is provided herein which includes a blend ofat least one natural alkali metal petroleum sulfonate, and at least onesynthetic alkali metal sulfonate. Preferably, the blend includes atleast about 30% by weight of a synthetic alkali metal sulfonateincluding at least about 30% by weight of alkali metal brancheddodecylxylene sulfonate having an equivalent weight of from about 500 toabout 550.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENT(S)

The present invention relates to a blend of natural and synthetic alkalimetal sulfonates, preferably sodium sulfonates. Natural sodiumsulfonates are produced by the sulfonation of petroleum fractionsderived from naturally occurring crude oil. Synthetic sodium sulfonatesare produced by the sulfonation of selected hydrocarbon compounds suchas linear or branched alkyl or alkylaromatic compounds.

The following list of sulfonates in Table 1 is illustrative of thevarious sulfonates which can be blended to make a product that hasemulsion performance equal to, or better than, that of Shell Reg (465).The sulfonates are commercially available and are provided withdesignations herein for purposes of identifying the sulfonatescorresponding to the test results in the Examples below.

Table 1

Sulfonate Description

-   -   Sulfonate A sodium salt of a straight chained mono- and        dialkylbenzene sulfonate with an equivalent weight of about 510        to about 530, preferably about 520    -   Sulfonate B sodium salt of a straight chained mono- and        dialkylbenzene sulfonate with an equivalent weight of about 420        to about 440, preferably about 430    -   Sulfonate C sodium salt of a straight chained mono- and        dialkylbenzene sulfonate with an equivalent weight of about 450        to 470, preferably about 460    -   Sulfonate D sodium salt of synthetic sulfonate with an        equivalent weight of about 480 to 500, preferably about 490    -   Sulfonate E sodium salt of the blend of sulfonates from a 600        SUS mineral oil, C₁₂-C₁₄ dialkylbenzene sulfonate and a C₂₀-C₂₄        mono alkylbenzene sulfonate with an equivalent weight of about        510 to about 530, preferably about 520    -   Sulfonate F sodium salt of a linear C₁₂-C₁₄ alkylxylene        sulfonate with an equivalent weight of about 370 to about 390,        preferably about 380    -   Sulfonate G sodium salt of a linear benzene sulfonate with an        equivalent weight of about 450 to about 470, preferably about        460    -   Sulfonate H sodium salt of a blend of sulfonates from a 600 SUS        mineral oil, C₁₂-C₁₄ dialkylbenzene sulfonate and a C₂₀-C₂₄ mono        alkylbenzene sulfonate with an equivalent weight of about 510 to        about 530, preferably about 520    -   Sulfonate I sodium salt of the sulfonate from a mineral oil        yielding an equivalent weight of about 540 to about 560,        preferably about 550    -   Sulfonate J sodium salt of a synthetic sulfonate    -   Sulfonate K sodium salt of a synthetic sulfonate    -   Sulfonate L sodium salt of a sulfonate    -   Sulfonate M sodium salt of a sulfonate from mineral oil with an        equivalent weight of about 440 to about 460, preferably about        450    -   Sulfonate N sodium salt of the sulfonate from mineral oil with        an equivalent weight of about 490 to about 510, preferably about        500    -   Sulfonate O sodium salt of tridecylbenzene sulfonate with an        equivalent weight of about 330 to about 350, preferably about        340    -   Sulfonate P sodium salt of dinonylnaphthalene sulfonate with an        equivalent weight of about 460 to about 480, preferably about        470    -   Sulfonate Q sodium salt of a sulfonate from a mineral oil        yielding an equivalent weight of about 450 to about 470,        preferably about 460    -   Sulfonate R sodium salt of a sulfonate from a mineral oil        yielding an equivalent weight of about 450 to about 470,        preferably about 460    -   Sulfonate S sodium salt of a sulfonate from a mineral oil        yielding an equivalent weight of about 410 to about 430,        preferably about 420    -   Sulfonate T sodium salt of the sulfonate from the co-sulfonation        of a 600 SUS mineral oil and straight chain dialkyl        (C₁₂-C₁₄)benzene sulfonate with an equivalent weight of about        515 to about 535, preferably about 527    -   Sulfonate U sodium salt of the co-sulfonation of mineral oil and        linear dodecylxylene blended with sodium dodecylbenzene        sulfonate and straight chained mono- and dialkylbenzene        sulfonate with a equivalent weight of about 420 to about 440,        preferably about 430    -   Sulfonate V sodium salt of a sulfonate from a mineral oil        yielding an equivalent weight of about 580 to about 600,        preferably about 590    -   Sulfonate W sodium salt of a sulfonate from a mineral oil        yielding an equivalent weight of about 450 to about 460,        preferably about 455    -   Sulfonate X sodium salt of a blend of sulfonates from a 600 SUS        mineral oil, C₁₂-C₁₄ dialkylbenzene sulfonate and a C₂₀-C₂₄ mono        alkylbenzene sulfonate with an equivalent weight of about 510 to        about 530, preferably about 520    -   Sulfonate Y sodium salt of a sulfonate from a mineral oil        yielding an equivalent weight of about 560 to about 570,        preferably about 565    -   Sulfonate Z sodium salt of a sulfonate from a mineral oil        yielding an equivalent weight of about 450 to about 470,        preferably about 460    -   Sulfonate AA sodium salt of an alkylaromatic sulfonate with an        equivalent weight of about 510 to about 530, preferably about        520    -   Sulfonate AB sodium salt of a branched dodecylortho-xylene        sulfonate with an equivalent weight of about 380 to about 400,        preferably about 390

Synthetic sodium sulfonates suitable for use in such blends includeSulfonate AA, a sodium salt of an alkyl aromatic sulfonate having anequivalent weight (“EW”) of about 520, and/or Sulfonate AB, a sodiumsalt of a branched dodecyl orthoxylene sulfonate having an equivalentweight of about 390. A preferred blend includes at least about 30% byweight of a sodium salt of Sulfonate AA, preferably from about 40% to90%, and yet more preferably from about 50% to 80%.

Suitable examples of natural sodium sulfonates can include, for example,Sulfonate S, a low molecular weight (420 EW) sodium petroleum sulfonate,and Sulfonate R, a medium molecular weight (460 EW) sodium petroleumsulfonate. Also suitable as a source of natural sodium sulfonate isSulfonate T, the product of the sulfonation of a blend of 600 SUSpetroleum oil (56-59 wt %) and a straight chain C₁₂-C₁₄ dialkylbenzenealkylate.

The proportions of natural and synthetic sulfonates present in theemulsifier blends can vary widely. In general, the emulsifier blendprepared in accordance with this invention can contain from about 10 toabout 70, preferably from about 20 to about 60, and more preferably fromabout 30 to about 50, weight percent natural petroleum sulfonateemulsifier(s), the remainder of the emulsifier blend being made up ofthe synthetic emulsifier(s).

To prepare a water-miscible lubricating oil concentrate, a sufficientamount of emulsifier blend as described above is substantially uniformlyadmixed with a quantity of lubricating oil (“base oil”) such that uponaddition of an aqueous medium thereto a stable oil-in-water emulsionwill result.

Preferred lubricating oils have a kinematic viscosity in the range offrom 1 to about 1,000 cSt at a temperature of 40° C. Suitablelubricating oils include mineral oils and synthetic oils. Examples ofmineral oils include a distilled oil which can be obtained by distillinga paraffinic crude oil, an intermediate crude oil or a naphthenic crudeoil under atmospheric pressure, or by distilling, under reducedpressure, a residual oil at the time of distillation under atmosphericpressure, and a refined oil obtained by refining this distilled oil.Examples of the refined oil include a solvent-refined oil, ahydrogenation-refined oil, a dewaxed oil and a clay-treated oil.Examples of synthetic oils include a low-molecular weight polybutene, alow-molecular weight polypropylene, oligomers of a-olefins having 8 to14 carbon atoms and hydrides thereof, alkylbenzenes, andalkylnaphthalenes. These mineral oils and synthetic oils can be usedsingly or in a combination of two or more thereof.

It is preferred that the lubricating oil contain from about 20 percentto about 60 percent by weight of a highly refined base oil having akinematic viscosity of from about 30 to about 800 cSt at a temperatureof 40° C., for example, a mineral oil having a sulfur content of about500 ppm or less, preferably about 100 ppm or less, treated by ahydrogenation-refining process and/or a (co)polymer of an olefin,because the employment of the highly refined base oil tends to inhibitthe generation of stains and rust on worked articles.

The amount of emulsifier blend to be added to a given weight oflubricating oil will, of course, depend on the nature of the emulsifierblend, the nature of the lubricating oil and other factors as thoseskilled in the art will readily appreciate. Optimum amounts of aparticular emulsifier blend and a particular lubricating oil can bedetermined employing routine testing methods. In general, a lubricatingoil concentrate in accordance with this invention can contain from 1 toabout 50, preferably from 2 to about 30, and more preferably from about5 to about 20, weight percent of emulsifier blend herein. Thelubricating oil, in addition to the emulsifier blend, can contain up toabout 10 weight percent fatty acid soap(s), up to about 10 weightpercent extreme pressure lubricating agent(s), up to about 5 weightpercent anti-corrosion agent(s) and up to 3 weight percent of one ormore biostatic and/or biocidal agents. Such additives are well known tothose with skill in the art and are commonly available.

The water-miscible lubricating oil concentrate herein upon addition toan aqueous medium, usually water, forms a stable aqueous emulsionsuitable for a variety of applications, metalworking principally amongstthem. Aqueous emulsions of the oil-in-water and water-in-oil type can beformed with the addition of from about 1 to about 50, preferably fromabout 2 to about 30 and more preferably from about 3 to about 20 weightparts of lubricating oil concentrate herein per 100 weight parts ofwater.

The following experimental results illustrate various aspects of theinvention including blends which performed successfully and blends whichdid not form satisfactory emulsions. Evaluation of the emulsionperformance of various blends was performed in accordance with thefollowing method.

Samples were diluted in white mineral oil at a 6% sulfonate level. Thesulfonates in white oil were tested alone (100%) and in blends ofsulfonates at 10 wt % intervals from 10 to 90% for emulsion performance.The emulsion test method used 10 mls of the test blend emulsified in 90mls deionized water by shaking a stoppered graduated cylinder. Theemulsions were rated after 24 hours. The rating system employed was zeroto 5 with zero representing an emulsion that had no distinct separationbetween any cream and the emulsion layer. The rating of 5 indicated anearly complete separation or oil and water with little or no hazinessin the water layer. The following numerical rating scale was used. TABLE2 Emulsion Rating Scale Rating Description 0 Superior - completely whiteemulsion with little or no separation 0.5 1 Excellent - white cream withwhite milky emulsion layer 1.5 2 Good - trace oil, with white milkyemulsion layer. 2.5 3 Fair - small oil layer, weak milky emulsion layer3.5 4 Poor - oil layer, skim milky emulsion layer 4.5 5 Negative - oillayer, possible small white cream layer, watery emulsion layer

The emulsion results and equivalent weights for the unblended sulfonatesare given in Table 2. Of the unblended 22 sulfonates tested, onlySulfonate AA and Sulfonate U gave emulsions. Sulfonate AA wasunexpectedly good considering its high molecular weight (520) and wassimilar to petroleum derived products like Sulfonate S or Sulfonate Q.TABLE 3 Emulsion Results for Sulfonates Equivalent Sulfonate RatingWeight Type of Sulfonate Sulfonate AA 0.5 520 Branched dodecylxyleneSulfonate U 2.5 420 Blend Sulfonate AB 4.5 390 Alkylaromatic Sulfonate F5 390 Linear dodecylxylene Sulfonate B 5 390 Alkylaromatic Sulfonate C 5395 Alkylaromatic Sulfonate J 5 Low Alkylaromatic Sulfonate M 5 445Petroleum Sulfonate K 5 Medium Alkylaromatic Sulfonate W 5 458 PetroleumSulfonate G 5 460 Alkylaromatic Sulfonate L 5 461 Sulfonate P 5 485Dialkylnaphthalene Sulfonate D 5 490 Synthetic Sulfonate N 5 500Petroleum Sulfonate E 5 510 Blend Sulfonate H 5 510 Blend Sulfonate X 5510 Blend Sulfonate I 5 540 Petroleum Sulfonate Y 5 540 PetroleumSulfonate V 5 600 Petroleum Sulfonate A 49 mls emulsion & 520Alkylaromatic 51 mls water

Various binary blends were tested for emulsion performance. Table 4illustrates the best performing blends of those tested, and is acompilation of Tables 3 and 5 through 14. TABLE 4 Best Binary Blends %of % of Sulfonate 1 Sulfonate 2 Sulfonate 1 Sulfonate 2 Rating SulfonateAA — 100    0.5 ″ Sulfonate B 50 50 0 ″ Sulfonate E 90 10 0 ″ SulfonateI 80 20 0 ″ Sulfonate F 80 20 1-1.5 ″ Sulfonate J 80 20 0 ″ Sulfonate K60 40 2-2.5 ″ Sulfonate L 80 20 0.5 ″ Sulfonate M 40-80 60-20 1-1.5 ″Sulfonate N 40-80 60-20 1-1.5 ″ Sulfonate P 80 20 0 ″ Sulfonate V 90 101-1.5 ″ Sulfonate W 80 20 2-2.5 ″ Sulfonate X 90 10 0 ″ Sulfonate Y 9010 0 ″ Sulfonate E 80 20 2-2.5 ″ Sulfonate I 45 55 1-1.5 ″ Sulfonate V40 60 0 ″ Sulfonate U 90 10 2-2.5 ″ Sulfonate X 75 25 1-1.5 ″ SulfonateY 70 30 2-2.5

Of the above listed sulfonates, Sulfonate I, Sulfonate M, Sulfonate N,Sulfonate V, Sulfonate W and Sulfonate Y were natural sodium petroleumsulfonates.

Table 5 illustrates the emulsion test results of the combinations ofSulfonate AB with the various sulfonates listed above. As can be seen,Sulfonate AB produced stable emulsions when blended in certainproportions with Sulfonate AA, Sulfonate I, Sulfonate E, Sulfonate U,Sulfonate Y, Sulfonate X and Sulfonate V.

Table 6 illustrates the emulsion test results of the combinations ofSulfonate AA with the various sulfonates listed above. Sulfonate AAproduced stable emulsions when blended in certain proportions withSulfonate B, Sulfonate I, Sulfonate P, Sulfonate E, Sulfonate F,Sulfonate Y, Sulfonate L, Sulfonate X, Sulfonate V, Sulfonate W,Sulfonate J, Sulfonate K, Sulfonate M and Sulfonate N.

Tables 7 to 15 illustrate the emulsion test results for sulfonatecombinations with respectively Sulfonate F, Sulfonate Y, Sulfonate A,Sulfonate J, Sulfonate X, Sulfonate K, Sulfonate M, Sulfonate V andSulfonate G. As can be seen, none of these sulfonate blends providedsatisfactory emulsifier compositions.

Referring now to Table 16 below, binary blends with Sulfonate R werebest when the Sulfonate R was combined with Sulfonate AA, althoughSulfonate AB also provided satisfactory emulsion test results as well asSulfonate F, Sulfonate J, Sulfonate M and Sulfonate N. TABLE 5 Emulsionson Blends with Sulfonate AB % Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate nate nate nate nate natenate nate nate nate nate nate AB AB AA B C A D G I P E F 10 — 1.5 5 5 55 5 5 5 5 5 20 — 2 5 5 5 5 5 5 5 5 5 30 — 2.5 5 5 5 5 5 5 5 5 5 40 — 4 55 5 5 5 1 5 5 5 50 — 4 5 5 5 5 5 1.5 5 4 5 60 — 4.5 5 5 5 5 5 1.5 5 4.55 70 — 4.5 5 5 5 5 5 3 5 4.5 5 80 — 4.5 5 5 5 5 5 3.5 5 2.5 5 90 — 4.5 55 5 5 5 4 5 2.5 5 % Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate nate nate nate nate nate natenate nate nate nate nate AB U Y L X V W J K H M N 10 2.5 5 5 5 5 5 5 5 55 5 20 2.5 5 5 5 5 5 5 5 5 5 5 30 2.5 5 5 5 5 5 5 5 5 5 5 40 3 5 5 5 5 55 5 5 5 5 50 3 5 5 5 5 5 5 5 4 5 5 60 3 5 5 5 0 5 5 5 4 5 5 70 3 2.5 5 10.5 5 5 5 4.5 5 5 80 5 2.5 5 1 0.5 5 5 5 4.5 5 5 90 5 3 5 2.5 2.5 5 5 55 5 5(—) Same sulfonate(x) Results on another table

TABLE 6 Emulsions on Blends with Sulfonate AA % Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate natenate nate nate nate nate nate nate nate nate nate AA AB AA B C A D G I PE F 10 x — 5 4 5 5 5 5 5 5 4.5 20 x — 5 4 5 5 5 5 5 5 4 30 x — 4 4 5 5 55 5 5 2.5 40 x — 0.5 4 5 5 5 5 5 5 2.5 50 x — 0 4 5 5 4 5 5 5 2 60 x —0.5 5 4 5 4 2.5 5 5 2 70 x — 4 5 4 5 4 0 2.5 5 1 80 x — 5 5 4 5 4 0 1 51 90 x — 5 5 4 3 4 0 2.5 0 1 % Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate nate nate nate nate natenate nate nate nate nate nate AA U Y L X V W J K H M N 10 x 5 5 5 5 5 55 5 5 5 20 x 5 5 5 5 5 5 5 5 5 5 30 x 5 5 5 5 5 2.5 5 5 2.5 5 40 x 5 5 55 5 2.5 5 5 1 1 50 x 5 5 5 5 5 2.5 5 5 1 1 60 x 5 3 5 5 5 2 2.5 5 1 1 70x 5 2.5 5 5 5 1.5 2.5 5 1 1 80 x 1.5 0.5 2 2 2.5 1.5 2.5 5 1 1 90 x 0 10 1 2.5 2.5 2.5 5 2.5 2.5(—) Same sulfonate(x) Results on another table

TABLE 7 Emulsions on Blends with Sulfonate F % Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate natenate nate nate nate nate nate nate nate nate nate F AB AA B C A D G I PE F 10 x x 5 5 5 4.5 5 5 5 5 — 20 x x 5 5 5 4.5 5 5 5 5 — 30 x x 5 5 54.5 5 5 5 5 — 40 x x 5 5 5 5 5 5 5 5 — 50 x x 5 5 5 5 5 5 5 5 — 60 x x 55 5 5 5 4.5 5 5 — 70 x x 5 5 5 5 5 4 5 5 — 80 x x 5 5 5 5 5 4 5 4.5 — 90x x 5 5 5 5 5 4.5 5 4 — % Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate nate nate nate nate natenate nate nate nate nate nate F U Y L X V W J K H M N 10 20 30 40 50 6070 80 90(—) Same sulfonate(x) Results on another table

TABLE 8 Emulsions on Blends with Sulfonate Y % Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate natenate nate nate nate nate nate nate nate nate nate Y AB AA B C A D G I PE F 10 x x 5 x 20 x x 5 x 30 x x 5 x 40 x x 5 x 50 x x 5 x 60 x x 5 x 70x x 5 x 80 x x 5 x 90 x x 5 x % Sulfo- Sulfo- Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate nate nate natenate nate nate nate nate nate nate nate Y U Y L X V W J K H M N 10 — 5 55 5 5 5 20 — 5 5 5 5 5 5 30 — 5 5 5 5 5 5 40 — 5 5 5 5 5 5 50 — 5 5 5 55 5 60 — 5 5 5 5 5 5 70 — 5 5 5 5 5 5 80 — 5 5 5 5 5 5 90 — 5 5 5 5 5 5(—) Same sulfonate(x) Results on another table

TABLE 9 Emulsions of blends with Sulfonate A % Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate natenate nate nate nate nate nate nate nate nate nate A AB AA B C A D G I PE F 10 x x — x 20 x x — x 30 x x — x 40 x x — x 50 x x — x 60 x x — x 70x x — x 80 x x — x 90 x x — x % Sulfo- Sulfo- Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate nate nate natenate nate nate nate nate nate nate nate A U Y L X V W J K H M N 10 x 5 520 x 5 5 30 x 5 4 40 x 5 4 50 x 5 4 60 x 5 4 70 x 5 4 80 x 4 4 90 x 4 4(—) Same sulfonate(x) Results on another table

TABLE 10 Emulsions on Blends with Sulfonate J % Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate natenate nate nate nate nate nate nate nate nate nate J AB AA B C A D G I PE F 10 x x x 5 5 20 x x x 5 5 30 x x x 5 5 40 x x x 5 5 50 x x x 5 5 60x x x 5 5 70 x x x 5 5 80 x x x 5 5 90 x x x 5 5 % Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate natenate nate nate nate nate nate nate nate nate nate J U Y L X V W J K H MW 10 x 5 5 5 5 — 5 5 5 20 x 5 5 5 5 — 5 5 5 30 x 5 5 5 5 — 5 5 5 40 x 55 5 5 — 5 5 5 50 x 5 5 5 5 — 5 5 5 60 x 5 5 5 5 — 5 5 5 70 x 5 5 5 5 — 55 5 80 x 5 5 5 5 — 5 5 5 90 x 5 5 5 5 — 5 5 5(—) Same sulfonate(x) Results on another table

TABLE 11 Emulsions on Blends with Sulfonate X % Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate natenate nate nate nate nate nate nate nate nate nate X AB AA B C A D G I PE F 10 x x 5 5 20 x x 5 5 30 x x 5 5 40 x x 5 5 50 x x 5 5 60 x x 5 5 70x x 5 5 80 x x 5 5 90 x x 5 5 % Sulfo- Sulfo- Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate nate nate natenate nate nate nate nate nate nate nate X U Y L X V W J K H M N 10 x x —5 x 5 5 20 x x — 5 x 5 5 30 x x — 5 x 5 5 40 x x — 5 x 5 5 50 x x — 5 x5 5 60 x x — 5 x 5 5 70 x x — 5 x 5 5 80 x x — 5 x 5 5 90 x x — 5 x 5 5(—) Same sulfonate(x) Results on another table

TABLE 12 Emulsions on Blends with Sulfonate K % Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate natenate nate nate nate nate nate nate nate nate nate K AB AA B C A D G I PE F 10 x x x 5 5 20 x x x 5 5 30 x x x 5 5 40 x x x 5 5 50 x x x 5 5 60x x x 5 5 70 x x x 5 5 80 x x x 5 5 90 x x x 5 5 % Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate natenate nate nate nate nate nate nate nate nate nate K U Y L X V W J K H MN 10 x 5 x 5 x — 5 5 20 x 5 x 5 x — 5 5 30 x 5 x 5 x — 5 5 40 x 5 x 5 x— 5 5 50 x 5 x 5 x — 5 5 60 x 5 x 5 x — 5 5 70 x 5 x 5 x — 5 5 80 x 5 x5 x — 5 5 90 x 5 x 5 x — 5 5(—) Same sulfonate(x) Results on another table

TABLE 13 Emulsions on Blends with Sulfonate M % Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate natenate nate nate nate nate nate nate nate nate nate M AB AA B C A D G I PE F 10 x x 5 5 5 20 x x 5 5 5 30 x x 5 5 5 40 x x 5 5 5 50 x x 5 5 5 60x x 5 5 5 70 x x 5 5 5 80 x x 5 5 5 90 x x 5 5 5 % Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate natenate nate nate nate nate nate nate nate nate nate M U Y L X V W J K H MN 10 x x x x — 20 x x x x — 30 x x x x — 40 x x x x — 50 x x x x — 60 xx x x — 70 x x x x — 80 x x x x — 90 x x x x —(—) Same sulfonate(x) Results on another table

TABLE 14 Emulsions on Blends with Sulfonate V % Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- nate natenate nate nate nate nate nate nate nate nate nate V AB AA B C A D G I PE F 10 x x 5 20 x x 5 30 x x 5 40 x x 5 50 x x 5 60 x x 5 70 x x 5 80 xx 5 90 x x 5 % Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo- Sulfo-Sulfo- Sulfo- Sulfo- Sulfo- nate nate nate nate nate nate nate nate natenate nate nate V U Y L X V W J K H M N 10 x 5 x — x x 20 x 5 x — x x 30x 5 x — x x 40 x 5 x — x x 50 x 5 x — x x 60 x 5 x — x x 70 x 5 x — x x80 x 5 x — x x 90 x 5 x — x x(—) Same sulfonate(x) Results on another table

TABLE 15 Emulsions on Blends with Sulfonate G % Sulfonate G Sulfonate ABSulfonate AA Sulfonate B Sulfonate C Sulfonate A Sulfonate D Sulfonate GSulfonate I 10 x x — 20 x x — 30 x x — 40 x x — 50 x x — 60 x x — 70 x x— 80 x x — 90 x x — % Sulfonate G Sulfonate P Sulfonate E Sulfonate FSulfonate U Sulfonate Y Sulfonate L Sulfonate X Sulfonate V 10 x x 5 x x20 x x 5 x x 30 x x 5 x x 40 x x 5 x x 50 x x 5 x x 60 x x 5 x x 70 x x5 x x 80 x x 5 x x 90 x x 5 x x % Sulfonate G Sulfonate W Sulfonate JSulfonate K Sulfonate H Sulfonate M Sulfonate N 10 x x x 20 x x x 30 x xx 40 x x x 50 x x x 60 x x x 70 x x x 80 x x x 90 x x x(—) Same sulfonate(x) Results on another table

TABLE 16 Emulsions on Binary Blends with Sulfonate R % Sulfonate RSulfonate AB Sulfonate AA Sulfonate B Sulfonate C Sulfonate A SulfonateD Sulfonate G Sulfonate I  0 4.5 0.5 5 ? 5 5 5 5 10 1.5 20 2.5 0 30 2.50 40 2.5 1.5 50 2.5 2.5 60 1.5 2.5 5 70 2.5 2.5 1.5 80 2.5 2.5 5 5 5 5 52 90 100  2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 % Sulfonate R Sulfonate PSulfonate E Sulfonate F Sulfonate U Sulfonate Y Sulfonate L Sulfonate XSulfonate V  0 5 5 2.5 5 5 5 5 5 10 20 4 30 40 4 50 3 60 2.5 70 2.5 80 55 1.5 5 5 5 5 5 90 1.5 100  2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 % SulfonateR Sulfonate W Sulfonate J Sulfonate K Sulfonate H Sulfonate M SulfonateN  0 5 5 5 5 5 10 20 5 30 2.5 40 1.5 5 5 50 1.5 3.5 5 60 1.5 5 2.5 3.570 2.5 5 1 3.5 80 5 2 2 5 2 2 90 1 1 1 100  2.5 2.5 2.5 2.5 2.5 2.500.51-1.5 Petronate L and HL-I2-2.5 Equal Equilon HL5 No emulsion

The natural alkali metal petroleum sulfonate can also be combined withmore than one synthetic alkali metal sulfonate in ternary mixtures. Forexample, Table 17 below sets forth emulsion test results for variouscombinations of Sulfonate R (natural sodium petroleum sulfonate) withSulfonate X and Sulfonate O. The designation “B&C” refers to quality ofblending and clarity. “Hazy/Sep” indicates a hazy condition withseparation of the emulsion. The emulsion ratings are as indicated above.TABLE 17 Ternary Blend to Sulfonate R Oil Blend Sulfonate R Sulfonate XSulfonate O Clarity Emulsion 100 0 0 B&C 2.5 90 0 10 B&C 2 85 0 15 B&C 280 0 20 Hazy/Sep 4.5 80 5 15 B&C 2 80 10 10 B&C 3 80 20 0 B&C 4.5 75 520 B&C 2.5 70 5 25 Hazy 2.5 70 10 20 B&C 2 70 20 10 B&C 5 65 10 25 B&C2.5 60 10 30 Hazy 5 60 15 25 B&C 3.5 60 20 20 B&C 4.5 55 20 25 B&C 3.550 15 35 Hazy/Sep 2.5 50 20 30 Hazy/Sep 2.5 50 25 25 B&C 3.5 50 30 20B&C 4.5 50 35 15 B&C 5 50 40 10 B&C 5 50 50 0 B&C 5

As can be seen, the best ternary mixtures were those in which thenatural petroleum Sulfonate R comprised at least about 50% of themixture and the amount of Sulfonate O exceeded the amount of SulfonateX.

While the above description contains many specifics, these specificsshould not be construed as limitations of the invention, but merely asexemplifications of preferred embodiments thereof.

1. An emulsifier composition comprising a blend of: a) at least onenatural alkali metal petroleum sulfonate; and b) at least one syntheticalkali metal sulfonate.
 2. The emulsifier composition of claim 1 whereinthe alkali metal is sodium.
 3. The emulsifier composition of claim 1wherein the synthetic alkali metal sulfonate is produced by thesulfonation of linear or branched alkyl or alkylaromatic compounds. 4.The emulsifier composition of claim 1 comprising at least 30% by weightof the synthetic alkali metal sulfonate.
 5. The emulsifier compositionof claim 1 wherein the synthetic alkali metal sulfonate comprises asynthetic sodium branched dodecylxylene sulfonate having an equivalentweight of from about 500 to about
 550. 6. The emulsifier composition ofclaim 1 comprises at least about 40% by weight of at least one syntheticsodium alkyl aromatic sulfonate having an equivalent weight of fromabout 350 to about 400 and wherein the natural alkali metal sulfonatecomprises at least one natural sodium petroleum sulfonate.
 7. Theemulsifier composition of claim 1 further comprising: c) an alkali metalsalt of a mixed natural and synthetic sulfonate blend.
 8. The emulsifiercomposition of claim 7 wherein the natural alkali metal sulfonateconstitutes at least 50% by weight of the emulsifier composition andcomprises the sodium salt of a sulfonate from a mineral oil yielding anequivalent weight of from about 450 to about
 470. 9. The composition ofclaim 8 wherein the alkali metal salt of the mixed natural and syntheticsulfonate blend comprises the sodium salt of a blend of sulfonates froma mineral oil, a C₁₂-C₁₄ dialkylbenzene sulfonate and a C₂₀-C₂₄monoalkylbenzene sulfonate with an equivalent weight of about 510 toabout
 530. 10. The composition of claim 9 wherein the synthetic alkalimetal sulfonate comprises a sodium salt of tridecylbenzene sulfonatehaving an equivalent weight of from about 330 to about
 350. 11. Thecomposition of claim 10 wherein the quantity of the of synthetic sodiumsalt of the tridecylbenzene sulfonate exceeds the quantity of the sodiumsalt of the mixed natural and synthetic sulfonate blend.
 12. Awater-miscible lubricating oil concentrate which comprises: a) at leastone oil of lubricating viscosity, and b) a blend of emulsifiers inadmixture with the oil in an amount sufficient to provide a stableaqueous emulsion upon the addition of an aqueous medium thereto, theblend of emulsifiers comprising: (i) at least one natural alkali metalpetroleum sulfonate; and, (ii) at least one synthetic alkali metalsulfonate.
 13. The water-miscible lubricating oil concentrate of claim12 wherein the oil of lubricating viscosity comprises a mineral and/orsynthetic lubricating oil selected from the group consisting of oilsobtained by the distillation of paraffinic crude oil, intermediate crudeoil, naphthenic crude oil, petroleum residue, solvent refined oils,hydrogenation refined oils, dewaxed oils, clay treated oils, lowmolecular weigh polybutene, low molecular weight polypropylene,oligomers of alpha-olefins having from about 8 to about 14 carbon atoms,alkylbenzenes, alkylnaphthalenes and combinations thereof.
 14. Thewater-miscible lubricating oil concentrate of claim 13 wherein the blendof emulsifiers constitutes from about 1% to about 50% by weight of theconcentrate.
 15. The water-miscible lubricating oil concentrate of claim13 further comprising one or more additives selected from the groupconsisting of fatty acid soap, extreme pressure additive, anticorrosionagents, biostatic agents and biocidal agents.
 16. The water-misciblelubricating oil concentrate of claim 13 wherein the synthetic alkalimetal sulfonate comprises one or more of a sodium branched dodecylxylenesulfonate, sodium dinonylnaphthalene sulfonate, sodium tridecylbenzenesulfonate, sodium dodecylbenzene sulfonate or sodium dialkylbenzenesulfonate.
 17. An aqueous lubricant oil-containing emulsion containing:a) water; and b) a water-miscible lubricating oil concentrate whichcomprises: i) at least one oil of lubricating viscosity, and ii) a blendof emulsifiers in admixture with the oil in an amount sufficient toprovide a stable aqueous emulsion upon the addition of an aqueous mediumthereto, the blend of emulsifiers including at least one natural alkalimetal petroleum sulfonate, and at least one synthetic alkali metalsulfonate.
 18. The aqueous lubricant oil-containing emulsion of claim 16wherein the blend of emulsifiers further includes an alkali metal saltof a mixed natural and synthetic sulfonate blend.
 19. The aqueouslubricant oil containing emulsion of claim 16, wherein said emulsion isa metalworking lubricant.